Liquid phase oxidation of paraffinic hydrocarbon mixtures



2,841,603 LIQUID PHASE ()XIDATION F PARAFFIYIC HYDROCARBONMIXTURES:

Carl N. Zellner, Berkeley Heights, and Fred'List'er, Cranf0rd,-N. J., assignors to-Tidewater Oil Company, a con poration of Delaware I v No Drawing. Application March 8, H SerialNo. 493,074

g 7 Claims. (CL 260-451) The present: invention relates to: a process for controlled; oxidation: of hydrocarbons and, particularly, to liquid phase partial oxidation of relatively high molecular weight predominantly paraffinic hydrocarbon mixtures with the use of anirnprovedoxida-t-ioncatalyst.

In the reaction'of. hydrocarbon: mixtures with. oxygen of a free oxygen-containing gas under oxidizing conditions for partial oxidation: of the mixtures, crude oxidized hydrocarbon mixtures are obtained that'comprise a wide variety of oxidizedproduct's', the nature of which appears to be primarily dependent upon theparticular conditions employed for effecting the oxidation. For example, the art contains numerous disclosures relating to partial oxidation of suitable hydrocarbon mixtures for preparation of acidic oxidized mixtures that possess relatively low l saponification values and contain a substantial amount of monobasic acids with a negligible amount, if any, of substances such as crystalline polyb'asic acids.

fication values (e. g. at least about 400 mgs. of KOH per gram, and higher) and contain a substantial amount of polyfunctional. acidic substances, including. crystalline dibasic acids. In illustration thereof, reference is made to U. S. Patent No. 2,486,454 disclosing a process for con,- trolled oxidation of suitable hydrocarbon mixtures in liquid phase by reaction thereof with oxygen of a free oxygen-containing gas for preparation of crude oxidized hydrocarbon mixtures that have a saponifi'cation value of at 'least 400, a substantial diiferenc'e between acid: and; saponification values, and contain a substantial amount of :p'olybasic acidic substances, including crystalline dibasic acids.

In the oxidation of. hydrocarbonsas aforesaid, it, is 4 desirable (1') that the oxidation reaction be carried out toagiven saponification value in as short a-time aspossible, (2) that the oxidation product be colorlessv or as nearly colorless as possible, and (3) that the oxidation product have a high ratio of acid to saponification'nnmher. A low color value is desirable as it facilitates preparation of colorless, or substantially colorless, derivatives such as esters of the acids in the oxidized mixture; an. accelerated rate of reactionis desirable as it enables; more efficient utilization of equipment used for: the oxidation reacti'oraandi an oxidation product as embodied herein havingja relatively high ratio; of acid: to saponifica'ti'on value is desirable as such products generally contain" a The art is also aware of processes for preparation of acidic oxidized hydrocarbon mixtures that possess relatively high saponirelatively high: amount: of desirable polyfunctional ma terials.

i The art is also aware of numerous materials that funcition as oxidation catalysts for carrying out partial oxidation. reactionsas aforediscussed witlr. specific catalysts 1, being metals such as cobalt, manganese, and others, pref erably in the form of compounds. thereof, that are soluble 2,841,503 Patented July 1, 1958 2 in the hydrocarbons subjected to oxidation. Of. such catalytic materials, manganese is particularly suitable in that oxidation reactions therewith can be carried out to relatively high saponification values at relatively fast rates of reaction. oxidation of relatively low molecular weight hydrocarbons, manganese salts of low molecular weight acids are usually preferred due to their solubility characteristics in such hydrocarbons, whereas; for liquid phase oxidation of relatively high molecular weight hydrocarbon mixtures, such as gas oils to paraffin waxes, manganese salts of relatively high molecular weight acids such as the higher fatty acids, naphthen'ic acids, andathe like, are generally preferred. Although manganese is, in general, suitable for oxidation of relativelyhigh' molecular weight hydrocarbon mixtures, a. desideratum is the obtainment of a catalyst material that will accelerate the rate of oxidation to a givenwsaponification value, and provide oxidation mixtures of suitable color and acid to saponification ratio. 7 The primary object of the present invention is to provide containing gas, of relatively high molecular Weight hydrocarbon. mixtures can be accelerated by use of an oxidation catalyst comprising manganese and ametal in group IVB of; the periodic table. In addition to accelerating the rate of the oxidation reaction, use of the combination catalyst as embodied herein generally" provides, for oxidation to comparable saponifi'cation values, oxidation products that are lower in color value. and/ or of higher ratio of acid to saponification. value than oxidation products obtained with the manganese catalysts per se.

In order to illustrate the invention in specific embodiments thereof, several tables are set forth hereinafter. The tabulated data is from oxidations made in accordance with the process described and claimed in U. S. Patent No. 2,486,454. In Tables I' to IV, inclusive, the data pertain to results obtained from liquid phase oxidation of a paraflin wax F'.,. melting point) at C. and an oxygen input rate of 6.0 liters per minute per kilogram of hydrocarbon charge. Properties of the wax used are as follows:

MANUFACTURED FROM A MIXTURE. OF EAST' TEXAS CRUDE AND PENNSYLVANIA CRUDE BY SWEATING Viscosity 210 F 36.0 Penetration 100g./77/5-'sees- 3'6- Oil content (wt. percent) 1.0 Tensile strength; 22" Color (Saybolt) 21 Table I. consists of such oxidations in which the catalyst consisted of a manganese catalyst per se or a group ence to the catalyst designated zirconium complex in Tables I, II, III and IV, said catalyst consisted of a zirconium complex salt of ethylene diamine' tetraacetic acid.

For certain oxidations, such as Table I Percent Gram atoms Saponification value-milli- Final catalyst of metal in grams KOH/g. ratio, Color, Run No. Catalyst (by weight catalyst per acid/ ASTM of charge) kilogram of sap. scale charge 3 hrs. 4% hrs. 6 hrs. 7% hrs 1 Manganese naphthenate (8% Mn)- 1.0 0. 0146 325 414 543 694 0. 63 3% 2-. do O. 0. 0073 280 364 426 454 0. 60 3% 3. do 0. 0. 0037 275 364 431 454 0. 6O 2% 4. Zirconium complex (6% Zr) 1. 5 0. 0000 185 314 386 485 0. 68 3% 6 Zirconium naphthenate (8% Zr)..- 1. 5 0. 0134 308 370 414 0.56 4

Table II, set forth hereinafter, illustrates embodiments of the invention using catalyst combinations of manganese and a group IVB metal, specifically thorium, titanium and zirconium. For purposes of comparison, Table II contains data for run No. 1 in which manganese naphthenate per so was used as the catalyst. As shown for run Nos. 6-9, inclusive, markedly higher saponification values were obtained by use of a combination catalyst as embodied herein, as compared to the results obtained with the manganese catalyst per se, thereby evidencing the accelerated rate of oxidation obtainable by practice of the invention described herein.

Table II, and (2) use of still another group IVB metal, hafnium. The marked improvement obtained by practice of the invention is clearly illustrated, particularly by comparison of the data for run Nos. 10 and 3 in Table III and Nos. 12 and 1 in Table IV as use of the combination catalyst produced a product of (1) higher saponification value, and (2) higheracid to saponification ratio after comparable times of reaction than were obtained in a corresponding run with the manganese catalyst per so. That such improvements over manganese per se results by use of a group IVB metal catalyst 7 Table II Percent Gram atoms Saponiflcation value-milli- Ratio, gflam catalyst of metal in grams KOH/g. atoms 11: Run N0. Catalyst (by weight catalyst per Group IVB of charge) kilogram of metal in catscharge 3 hrs. 4% hrs. 6 hrs. 7% hrs. lyst 1 Manganese naphthenate (8'2 Mn) 1.0 8. 851g 325 414 543 694 7 Manganese naphthenate (8% Mn) 0.0109 6 {Zirconium naphthenate (8% Zr) l 74 m 353 500 582 6 M hth t (87 M 0: anganese nap ena e n 0. 7 {Thorium naphthenate (21.25% Th)-.} 7 0 0172 363 510 600 5 M hth t (87 M 8 8%? anganese nap ena e n 8 {Titanium naphthenate (3%'I i) l 5 0 0198 365 506 588 M hth t (87 M g: anganese nap one o n 9 {Zirconium complex (6% f 1.5 m 366 510 620 682 1.0.9

In Tables III and IV, set forth hereinafter, data are in combination with manganese is clearly unexpected,

presented illustrating additional embodiments of the invention with (1) catalyst concentrations different than employed in the runs for which data are presented in especially in view of the aforeshown inferiority of zirconium per so as compared to manganese in catalyzing the oxidation reaction.

Table III Percent Gram atoms Saponification value- Final Ratio, gram catalyst of metal in milligrams KOH/g. ratio, Color. atoms Run N 0. Catalyst (by catalyst per acid/ ASTM MntGroup weight kilogram of sap. scale IVB metal of charge) charge 4% hrs. 6 hrs. 7% hrs. in catalyst 3 Manganese naphthenate (8% Mn) 0.25 0 92; 364 431 454 0. 2%

Manganese naphthenate (8? Mn) 0: 00273 I Hafnium naphthenate 6.7%110 0 387 488 599 3 5 M hth t (8 7 M anganese nap one o n 11 Zirconium c0mp1ex(3% I 4 56 Table IV Percent Gram atoms Saponiflcation value- Final Ratio, gram catalyst of metal in Milligrams KOH/g. ratio Color, atoms Run No. Catalyst (by catalyst per acid] ASTM Mn: Group weight kilogram of sap. scale IVB metal of charge) charge 3 hrs. 4% hrs. 6 hrs. 7% hrs. in catalyst 1.' Manganese naphthenate (8% Mn)... 1. 0 8. 858 325 414 543 594 0. 63 3% Manganese naphthenate (8? Mn)... 0: 0032 i 12 Zirconium naphthenate 1.2 338 633 650 0.66 1% 1 0.27

M hth t (87 M amanese nap ena e n 13 zircoiium naphthenate 1.26 30 386 533 650 0.66 1% 1.0.9 0. 01

Regarding hydrocarbon charge stoeksfor carrying out oxidation reactions as embodied herein, 'stock s that are predominantly'paralfinic are, preferred. As aforesaid, the invention contemplates oxidation of relatively high charge have been shown, it should be understood'that such concentrations have been utilized for purposes of illustration and not limitation. 'It should be clear to those skilled in the art that catalyst concentrations other 7 molecular Weight hydrocarbon materials, such, for exthan those specifically set forth herein may be employed ample, liquid to solid petroleum fractions varying from with obtainment of the desired results dependent on gas oils to paraifin -waxe :and including. i te di t factors such as the'particular hydrocarbon mixture to fraction u h as l k waxes, S h an b dj t f be oxidized and the reaction conditions employed. the invention is "illustrated by following Table V' contain- Moreover, although the combination catalysts set forth i d eb in d by b id i f Slack x i a l0 hereinbefore for illustrative purposes comprised specific refined by filtration through filter clays under the reaction ratios Of fl l 9 group IVB metal: it Should be conditions f oxygen input and temperature utilized clear to those skilled 1n the art that the invention may for the oxidation runs of the. preceding tables. As shown b PIaCticed with difielent Tail of group 1V3 metal in Table V,v use of the combination catalyst asembodied to manganese as long 1 ratio p y is Such that h ei markedly l t d th rate f reaction d the rate of oxidations carried out therewith are accelerated produced an oxidation product of higher acid to saponifias compared to use per se of the manganese component cation ratio than that obtained with the manganese catalyst of the combination catalyst. Although it is not intended per se. that the invention be limited to catalysts of defined Table V Percent Gram atoms Saponlflcatlon value- Final Ratio, gram Run catalyst of metal in Milligrams KOH/g. ratio atoms No. Catalyst (by catalyst per acld/ Mn: Group weight kilogram of sap. IVB metal 0! charge) charge 4% hrs. Ghrs. 7% hrs. lncatalyst 14--...-.. Manganese naphthenate (8% Mn) 1.0 386 482 554 0.60 15 gt ggqggi ggggg ga gga{@ 1.5 M066 401 560 650 0.64 1:0.9

As is further evident from the data in the foregoing numerical ratio as to weight of the group IVB metal tables, use of the combination catalyst as embodied herein to manganese in the combination catalyst, the ratio of accelerates the oxidation reaction at both relatively low manganese to group IVB metal may be in amounts within and relatively high saponification values. In a particular the range of one gram atom of manganese to from about embodiment, the invention is directed to liquid phase to about gram atoms 0f the group IVB metal oxidation of predominantly paraffiuic relatively high Sulficient to Provide the Synergistic effect as aforemolecular weight hydrocarbon mixtures to saponification described as Compared to the use of the manganese Salt values of at least 400 to produce oxidized mixtures con- P most purposes, however, Suitable Iesults taining a substantial amount of polyfunctional materials are provldefl by use of a T3110 of manganese to g p including crystalline dibasic acids. In illustration thereof, IVB metal 111 the range of one gram atom of manganese the invention may be carried out with respect to the to from about to about 2 gram atoms of the gTouP oxidation reaction in accordance with the process de- IVE metal scribed in U. s. Patent No. 2,486,454, the disclosure of Althqugh Present i has been desFnbed which is incorporated herein by reference, relating to comunctlon ,Wlth preierred fimbodlmepts partial oxidation of predominantly paralfinic hydrocarbon thereof ,m Sklued F W111 readlly recogmze mixtures in liquid phase by contacting such a mixture with that i and mpdificafions can be q Such a free oxygen-containing gas under controlled conditions modlficaitlons and .vanatlons are consldered to to cause combination of oxygen withthe hydrocarbon be Wlthm the New of the Speclficafion and Scope of mixture at an average rate related to the oxidizing temi gig sf clalms' are. assure salsa-50:2 :5 1-111 of oxidizing temperature of 120 C., substantially above 23 mPIecular Welght predommanfly Parafiimc hyqrpcarbon liters of oxygen per hour per kilogram of hydrocarbons E i with Ki i czltallnng at an oxidizing temperature of 150 C., and substantially g n:npwvemen w erem 6 02m 21.1011 on is Cain-5e above 135 mars of oxygen per hour per kilagram 0f out in the presence of an oxidation cata yst consisting essentlally of a combmation of manganese and a group hydrlmarbons at an Oxldlzmg iemiaeramre of 180 I IVB metal in ratio of one gram atom of manganese- W reference P the combmatlqn catalyt F F 0 to from about 0.1 to about 2.5 gram atoms of the group herein and comprising manganese 1n comblnatlon w1th IVB metaL a group IVB metal, and 1n the use thereof 1n the form of 2 In the liquid phase oxidation of relatively high salts i amon component or i f 9 the salts molecular weight predominantly paraffinic hydrocarbon are desirably such that the combination oxldation catalyst mixtures with oxygen of a freeflxygfin Containing gas, 18 Soluble at least i amounts Suitable .Such m the improvement wherein the oxidation reaction is carried the lpfdmcarbm mlxture. unfier the reactlon out in the presence of an oxidation catalyst consisting 5212 35: 5; gfig i gi fg fsg fgf i iz zs gg essentially of a combination of a manganese salt of a relatively high molecular weight organic acids such as hlgh mclecuiar f orgamc i and IVB fatty acids, naphthenic acids, and others, with specific ilp salt OI a lilgh moleciflar Welgh? orgamc acld the lustrations of the fatty acids being those of the fatty acid ratio of Salts bemg such mat there 15 one gram atom series containing from about eight to about twenty-four cf manganess to from about to about gram atoms carbon atoms and including laurie acid, stearic acid, and of the group IVB metal- 1 others 3. In the liquid phase oxidation of relatively high Alth u h, in the foreg in xam le specific eeneenmolecular weight predominantly paraflinic hydrocarbon trations of catalysts, based on the weight of hydrocarbon mixtures with oxygen of a free-oxygen containing gas to produce an acidic, partially oxidized product having a saponification value of at least about 400 and a substantial difference between acid and saponification values, the improvement wherein the oxidation reaction is carried out in the presence of an oxidation catalyst consisting essentially of a combination of manganese and a group IVB metal in ratio of one gram atom of manganese to from about 0.1 to about 2.5 gram atoms of the group IVB metal.

4. The improvement as defined in claim 1 except that the said ratio is one gram atom of manganese to from about 0.25 to 2 gram atoms of group IVB metal.

5. The improvement as defined in claim 2 except that the said ratio is one gram atom of manganese to from about 0.25 to 2 gram atoms of group IVB metal.

6. The improvement as defined in claim 1 wherein the group IVB metal is a member of the group consisting of titanium, zirconium, hafnium and thorium.

7. The improvement as defined in claim 1 wherein the group IVB metal is zirconium.

References Cited in the file of this patent V UNITED STATES PATENTS 

1. IN THE LIQUID PHASE OXIDATION OF RELATIVELY HIGH MOLECULAR WEIGHT PREDOMINANTLY PARAFFINIC HYDROCARBON MIXTURES WITH OXYGEN OF A FREE-OXYGEN CONTAINING GAS, THE IMPROVEMENT WHEREIN THE OXIDATION REACTION IS CARRIED OUT IN THE PRESENCE OF AN OXIDATION CATALYST CONSISTING ESSENTIALLY OF A COMBINATION OF MANGANESE AND A GROUP IVB METAL IN RATIO OF ONE GRAM ATOM OF MANGANESE TO FROM ABOUT 0.1 TO ABOUT 2.5 GRAM ATOMS OF THE GROUP IVB METAL. 